CN105924611A - Low-viscosity OH prepolymer and preparing method thereof - Google Patents
Low-viscosity OH prepolymer and preparing method thereof Download PDFInfo
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- CN105924611A CN105924611A CN201610289367.9A CN201610289367A CN105924611A CN 105924611 A CN105924611 A CN 105924611A CN 201610289367 A CN201610289367 A CN 201610289367A CN 105924611 A CN105924611 A CN 105924611A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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Abstract
The invention discloses a low-viscosity OH prepolymer and a preparing method thereof. The low-viscosity OH prepolymer contains copolyester polyol, wherein the viscosity of copolyester polyol at 25 DEG C ranges from 500 mPa.s to 3000 mPa.s, the number-average molecular weight Mn ranges from 2000 to 3000, the disersity PDI ranges from 1.2 to 1.8, and the acid value is smaller than or equal to 1.5 mg/gKOH. The low-viscosity OH prepolymer overcomes the defect that due to large viscosity of an existing high molecular weight polyester polyol prepolymer, synthesis of a solvent-free polyurethane material is influenced; when the low-viscosity OH prepolymer is used for preparing solvent-free polyurethane, the dosage of a polyether polyol thinning agent can be effectively reduced, and the performance of the solvent-free polyurethane material can be improved.
Description
Technical field
The application relates to a kind of low viscosity OH performed polymer and preparation method thereof, belongs to polyurethane material system
Standby field.
Background technology
Polyurethane material have excellence mechanical performance, the high modulus of resilience, stable chemical property,
Good water resistance, good chemical resistance and there is preferable biocompatible, meanwhile,
Polyurethane material can be by changing the structure of isocyanates or by changing the soft of polyurethane segment
Toughness, thus obtain and there is the material of different performances and purposes, thus be widely used in production and
In sphere of life.
Since Bayer AG of Germany is since nineteen forty-one large-scale production polyurethane products, polyurethane work
Industry is developed rapidly.According to statistics, the global polyurethane between 2004 to 2014 years 10 years produces
2.5% can be reached by annual rate of growth, calculate by this growth rate, the global polyurethane production capacity by 2016
Will be more than 20000kt/a.At present, the production process of major part polyurethane material employs substantial amounts of have
Machine solvent, not only increases industrial cost, brings serious environmental pollution simultaneously, and can be serious
The health of infringement staff, therefore, no-solvent polyurethane synthetic technology based on reaction molding becomes
The study hotspot in this field.Abroad, start to have researched and developed no-solvent polyurethane material in the seventies,
The time of domestic research and development is later, but technical research speed is rapid.No-solvent polyurethane synthetic technology is not only
Reduce synthesis cost, more environment-friendly, make its range of application more wide simultaneously.
In no-solvent polyurethane synthetic technology, many OH base performed polymer and the conjunction of many NCO base performed polymer
One-tenth technology is crucial.The most conventional many OH base performed polymer is mainly polyether polyol performed polymer, should
Performed polymer has the advantage that molecular weight is high, viscosity is low, compliance is good, is very suitable for condition of no solvent
The synthesis of lower polyurethane.Patent US 6635723, EP-A-0712877, EP-A-0808859, DE-A
4011455 and Chinese patent CN 104072715, CN101280167 etc. use polyether polyol many
OH base performed polymer has synthesized the polyurethane material of multiple performance, but polyether material hot strength is low,
Wear no resistance and seriously limit its mechanical performance；Its use temperature of the low reduction of poor heat resistance glass transition temperature
Degree；Resistance to chemical reagents difference limits the applicable situation of product, shortens its service life simultaneously.
Generally, mechanical performance that PEPA has had compared with polyether polyol, high thermally-stabilised, good
Good drug-resistant performance, is therefore preferable polyurethane synthetic material, but high molecular weight polyesters is polynary
Alcohol material molecule rigidity is big compared with polyether material so that it is the higher poly-ammonia being unfavorable under condition of no solvent of viscosity
The synthesis of ester material.Therefore, how improving molecular weight and reducing its viscosity is that acquisition is preferable solvent-free poly-
The urethane synthesis key of PEPA polyhydroxy performed polymer.Patent US 6610779 uses polyester
Polyhydric alcohol performed polymer synthesis no-solvent polyurethane, but its viscosity during molecular weight of polyesters as little as 800g/mol
Just meet uninanned platform condition；Patent US 6787596 employs molecular weight as little as 1000 equally
The low viscosity polyester polyols performed polymer synthesis no-solvent polyurethane of g/mol；Patent CN101280167
The PEPA performed polymer using molecular weight to be 2000g/mol has synthesized no-solvent polyurethane, but
The polyether polyol that with the addition of nearly 50wt% in PEPA is glued to reduce it as diluent
Degree, although the addition of a large amount of polyether polyol diluent can reduce its viscosity well, but the most right
The performance of polyurethane material causes the biggest impact.
Therefore, synthesis high molecular low viscosity polyester polyols is to obtain high-performance no-solvent polyurethane material
The key of material.
Summary of the invention
An aspect according to the application, it is provided that a kind of low-viscosity polyurethane OH performed polymer, to overcome
High-molecular-weight poly ester polyol performed polymer viscosity is unfavorable for more greatly the conjunction of no-solvent polyurethane material at present
The defect become.Described low viscosity OH performed polymer, for the preparation of no-solvent polyurethane, can effectively drop
The usage amount of oligomeric ethers polyol diluent, improves the performance of no-solvent polyurethane material.
Described low viscosity OH performed polymer, it is characterised in that contain in described low viscosity OH performed polymer
Copolyester polyols；
Described copolyester polyols by least one in the dicarboxylic acids with structural formula shown in Formulas I with
At least one polymerization having in the dihydroxylic alcohols of structural formula shown in Formula II obtains:
In Formulas I, n is 0 or 1；A1Selected from the alkylidene that carbon number is 1～8；
In Formula II, m is selected from 0,1,2 or 3；A2Being selected from carbon number selected from carbon number is 1～8
Alkylidene.
Preferably, viscosity=500 of described copolyester polyols 25 DEG C～3000mPa s；
Number-average molecular weight Mn=2000 of copolyester polyols～3000；
The dispersion PDI=1.2～1.8 of copolyester polyols；
The acid number of copolyester polyols≤1.5mg/g KOH.
In the application, described alkylidene is to lose any two hydrogen atom institute shape on alkane compound molecule
The group become.Described alkane compound includes linear paraffin, with the alkane of side chain and cycloalkane.
Another aspect according to the application, it is provided that the preparation method of above-mentioned low viscosity OH performed polymer, its
It is characterised by, comprises the following steps:
A) raw material containing copolyester polyols, diluent, chain extender and cross-linking agent is placed in 85～
100 DEG C of vacuum drying；
B) system temperature is down to 40～50 DEG C, after adding catalyst I and defoamer, keeps 40～50 DEG C
At a temperature of vacuum froth breaking no less than 0.5 hour, i.e. obtain described low viscosity OH performed polymer；
Wherein, employed in step a) and step b), the weight proportion of raw material is:
Copolyester polyols: 75～90 weight portions；
Diluent: 5～20 weight portions；
Chain extender: 2～5 weight portions；
Cross-linking agent: 1～3 weight portions；
Catalyst I:0.01～0.5 weight portion；
Defoamer: 0.01～0.1 weight portion.
Described diluent is in polypropylene glycol, PolyTHF dihydroxylic alcohols, polypropylene oxide trihydroxylic alcohol
At least one；Preferably, described diluent is selected from poly-the third two that number-average molecular weight is 200～3000
Alcohol, number-average molecular weight be 1000～2000 PolyTHF dihydroxylic alcohols, number-average molecular weight be
At least one in the polypropylene oxide trihydroxylic alcohol of 350～3000；It is further preferred that described diluent
Selected from polypropylene glycol, number that the polypropylene glycol that number-average molecular weight is 1500, number-average molecular weight are 200
PolyTHF dihydroxylic alcohols that polypropylene glycol that average molecular weight is 3000, number-average molecular weight are 1000,
The polyoxygenated third that PolyTHF dihydroxylic alcohols that number-average molecular weight is 2000, number-average molecular weight are 350
Alkene trihydroxylic alcohol, number-average molecular weight are at least one in the polypropylene oxide trihydroxylic alcohol of 3000.
Preferably, at least during described chain extender is selected from the dihydroxylic alcohols with structural formula shown in Formula II
Kind.It is further preferred that described chain extender is selected from ethylene glycol, 1,3-PD, BDO, new
At least one in pentanediol, hexane diol.
Preferably, at least during described cross-linking agent is selected from alcohol compound and/or alcamine compound
Kind.It is further preferred that described cross-linking agent is selected from glycerol, tetramethylolmethane, diethanolamine, N-
At least one in methyl diethanolamine, N-ethyldiethanolamine, N butyl diethanol amine.
Preferably, described catalyst I is selected from dibutyl tin laurate, double (2-dimethylaminoethyls)
Ether, N, at least one in N '-dimethyl pyridine, 1,8-diazabicylo 11 carbon-7-alkene.
Preferably, described defoamer is modification organic silicon oil.
Preferably, described copolyester polyols uses esterifying polycondensation reaction preparation, comprises the following steps:
(1) by containing at least one having in the dicarboxylic acids of structural formula shown in Formulas I, there is formula
In the dihydroxylic alcohols of structural formula shown in II at least one, the raw material of catalyst II, auxiliary agent be placed in point
In the reaction vessel of water device, N2Under protection, react 2～4 hours at a temperature of 130～150 DEG C,
And remove the water generated in reaction with water entrainer simultaneously；
(2), after step (1) terminates, system temperature is increased to 155～180 DEG C, N2Continue under protection
Continuous reaction also removes the water generated in reaction simultaneously with water entrainer, after reacting 2～4 hours, removes band
Water preparation；
(3), after step (2) terminates, system temperature is increased to 180～200 DEG C of vacuum decompressions except water
2～4 hours, i.e. obtain described copolyester polyols.
Preferably, step (1) has the dicarboxylic acids of structural formula shown in Formulas I and there is Formula II institute
The molar ratio showing the dihydroxylic alcohols of structural formula is:
There is the dicarboxylic acids of structural formula shown in Formulas I: there is the dihydroxylic alcohols of structural formula shown in Formula II
=1:1.0～1.3.
Preferably, have described in the dicarboxylic acids of structural formula shown in Formulas I selected from adipic acid, SA,
At least one in suberic acid.
Preferably, have described in the dihydroxylic alcohols of structural formula shown in Formula II selected from ethylene glycol, 1,3-PD,
In 1,4-butanediol, neopentyl glycol, hexane diol, diethylene glycol, dipropylene glycol, triethylene glycol
At least one.
Preferably, at least during catalyst II described in step (1) is selected from titanate ester compound
Kind.It is further preferred that described catalyst II is selected from butyl titanate, tetra isopropyl titanate, titanium
At least one in acid four methyl ester, metatitanic acid orthocarbonate.
Preferably, described in step (1), catalyst II weight/mass percentage composition in the feed is
0.002wt%～0.01wt%.
Preferably, described in step (1), auxiliary agent is triphenylphosphine.
Preferably, described in step (1), auxiliary agent weight/mass percentage composition in the feed is
0.005wt%～0.02wt%.
Preferably, described water entrainer is toluene.Division box is to connect one on reaction vessel limit to return
Stream device, the toluene condensed out and water stratification, lower layer of water releasing, upper toluene Returning reacting system
Continue band water.
Another aspect according to the application, it is provided that the method preparing polyurethane material, it is characterised in that
By the polyisocyanates containing 45～50 weight portions, 30～35 weight of polyester diatomic alcohol compounds, 25～30
Weight portion polyether Glycols compound, 0.01～1 catalyst III, 0.8～1.1 weight portion of weight portion
The raw material mix homogeneously of chain extender, after adding 100 weight portion low viscosity OH performed polymers mix homogeneously,
It is placed in 80～120 DEG C of dry solidifications, i.e. obtains polyurethane material；
Described low viscosity OH performed polymer is selected from any of the above-described low viscosity OH performed polymer, according to above-mentioned
At least one in the low viscosity OH performed polymer that one method prepares.
Preferably, described polyisocyanates is selected from isophorone diisocyanate and/or 4,4-dicyclohexyl
Methane diisocyanate.
Described polyester binary alcoholic compound is PCDL.
Described polyether Glycols compound is PTMG dihydroxylic alcohols.
Described catalyst III is 1,8-diazabicylo 11 carbon-7-alkene.
Described chain extender is 1,4-butanediol and/or 1,6-HD.
The beneficial effect of the application includes but not limited to:
(1) the low-viscosity polyurethane OH performed polymer that the application provides, overcomes current high molecular
PEPA performed polymer viscosity is unfavorable for more greatly the defect of the synthesis of no-solvent polyurethane material.
(2) preparation method of the low-viscosity polyurethane OH performed polymer that the application provides, prepared
Low-viscosity polyurethane OH performed polymer, for the preparation of no-solvent polyurethane, can effectively reduce polyethers
The usage amount of polyol diluent, improves the performance of no-solvent polyurethane material.
Accompanying drawing explanation
The Fourier transform infrared spectroscopy figure of Fig. 1 sample A1.
Detailed description of the invention
Below in conjunction with embodiment in detail the application is described in detail, but the application is not limited to these embodiments.
If no special instructions, the raw material in embodiment and test condition are as follows:
The adipic acid of employing, SA, suberic acid, polypropylene glycol-1500, polypropylene glycol in embodiment
-200, polypropylene glycol-3000, PolyTHF dihydroxylic alcohols-1000, oxolane dihydroxylic alcohols-2000,
Diethanolamine, N methyldiethanol amine, N-ethyldiethanolamine, N butyl diethanol amine, triphenyl
Phosphine (being abbreviated as TPP) is analytical pure, purchased from Aladdin Reagent Company；Dimethylbenzene, toluene, change
Property organic silicone oil is analytical pure, purchased from Chemical Reagent Co., Ltd., Sinopharm Group；Butyl titanate,
Tetra isopropyl titanate, metatitanic acid four methyl ester, metatitanic acid orthocarbonate are analytical pure, purchased from lark prestige reagent；
1,8-diazabicylo 11 carbon-7-alkene, dibutyl tin laurate, N, N '-dimethyl pyridine is point
Analyse pure, purchased from Ti Xiai Reagent Company of Japan.
The Fourier transform infrared spectroscopy of sample is infrared in the Vertex-70-FT-IR type of Bruker company
Measure on spectrogrph.
The viscosity of sample uses NDJ-4 rotary viscosimeter (Shanghai Ping Xuan scientific instrument company limited)
Measure at 25 DEG C.
The mean molecular weight of sample is by Waters BreezeTM2HPLC high-performance liquid chromatogram determination.
Sample dispersion degree PDI is by Waters BreezeTM2HPLC high-performance liquid chromatogram determination.
Sample acidity uses GB HG/T2708-1995 standard determination method to measure.
The preparation of embodiment 1 copolyester polyols sample A1
1,4-butanediol and the 5.59g of 24.33g (0.27mol) is added in dry there-necked flask
(0.09mol) ethylene glycol, installs condensing unit, logical N2Protection, is warming up to 130 DEG C, starts to stir
Mix.The adipic acid accurately weighing 43.84g (0.3mol) is dividedly in some parts in reaction bulb, stirs 15 minutes
All dissolving to solid, solution is water white transparency shape.Water knockout drum is now installed, by accurately measure
The additive triphenylphosphine of 0.0114g, 0.0048g butyl titanate add in reaction bulb, are subsequently adding
15～20ml toluene, strengthen N2Flow, reacts 2～4 hours at this temperature, until taking out of big
The water of about 80% (is calculated by the amount reacting generated water completely in theory by binary acid), now steams
Go out toluene；It is to slowly warm up to 160 DEG C, then adds 15～20ml dimethylbenzene, at this in reaction system
Temperature react 2～4 hours, until take out of about 15% water (the completeest by binary acid
The amount of the water that full response is generated calculates), now steam dimethylbenzene；Remove band water device, use instead and subtract
Pressure distilling apparatus, rises to 180 DEG C simultaneously by temperature, in the reaction decompression distillation of this temperature, simultaneously
Detection system acid number, stopped reaction after acid number is down to 1.5mg/g KOH；Treat temperature be down to 40～
80 DEG C, pour into rapidly and drying receptacle seals preservation, be designated as copolyester polyols sample A1.
Sample A1 is carried out Fourier transform infrared spectroscopy diffraction analysis, and result is as shown in Figure 1.By
Figure is it can be seen that at 1733cm-1Locate the stretching vibration peak for C=O, at 2955cm-1Place is-OH
Stretching vibration.
Measuring the viscosity of sample A1, result is: 2800mPa s.
Measuring the average molecular weight of sample A1, result is: Mn=2650.
Measuring the dispersion of sample A1, result is: DPI=1.65.
The preparation of embodiment 2 copolyester polyols sample A2
The 1,4-hexanediol of 23.64g (0.20mol), 5.59g is added in dry there-necked flask
(0.09mol) ethylene glycol, the diethylene glycol of 7.43g (0.07mol), installs condensing unit, logical N2
Protection, is warming up to 140 DEG C, starts stirring.The adipic acid accurately weighing 43.84g (0.3mol) divides
Criticizing in addition reaction bulb, stir and all dissolve to solid for 15 minutes, solution is water white transparency shape.This
Time install water knockout drum, by the 0.0116g additive triphenylphosphine accurately measured, 0.0051g metatitanic acid four fourth
Ester adds in reaction bulb, is subsequently adding 15～20ml toluene, strengthens N2Flow, at this temperature
React 2～4 hours, until the water taking about 80% out of (is reacted institute in theory completely by binary acid
The amount of the water generated calculates), now steam toluene；It is to slowly warm up to 170 DEG C, then toward in reaction system
Adding 15～20ml dimethylbenzene, reacting 2～4 hours at this temperature, until taking about 15% out of
Water (being calculated by the amount reacting generated water completely in theory by binary acid), now steam diformazan
Benzene；Remove band water device, use vacuum distillation apparatus instead, temperature is risen to 195 DEG C, in this temperature simultaneously
Degree insulation reaction decompression distillation, detection system acid number simultaneously, stops after acid number is down to 1.5mg/g KOH
Only reaction；Treat that temperature is down to 40～80 DEG C, pour into rapidly and drying receptacle seals preservation, be designated as copolymerization
Ester polyol sample A2.
Sample A2 is carried out Fourier transform infrared spectroscopy diffraction analysis, and result is similar with Fig. 1,
1733cm-1There is the stretching vibration peak of C=O vicinity, at 2955cm-1Near have the flexible of-OH to shake
Move and be strong peak.
Measuring the viscosity of sample A2, result is: 2250mPa s.
Measuring the average molecular weight of sample A2, result is: Mn=2075.
Measuring the dispersion of sample A2, result is: DPI=1.79.
The preparation of embodiment 3 copolyester polyols sample A3
The diethylene glycol of 31.83g (0.30mol), 7.09g (0.06mol) is added in dry there-necked flask
Isosorbide-5-Nitrae-hexanediol, condensing unit, logical N are installed2Protection, is warming up to 130 DEG C, starts stirring.Accurate
The adipic acid really weighing 43.84g (0.3mol) is dividedly in some parts in reaction bulb, stirs 15 minutes to solid
All dissolving, solution is water white transparency shape.Water knockout drum is now installed, the 0.0114g that will accurately measure
Additive triphenylphosphine, 0.0048g butyl titanate add in reaction bulb, are subsequently adding 15～20ml
Toluene, strengthens N2Flow, reacts 2～4 hours at this temperature, until taking about 80% out of
Water (is calculated by the amount reacting generated water completely in theory by binary acid), now steams toluene；
It is to slowly warm up to 160 DEG C, then adds 15～20ml dimethylbenzene, at this temperature in reaction system
React 2～4 hours, until the water taking about 15% out of (is reacted institute in theory completely by binary acid
The amount of the water generated calculates), now steam dimethylbenzene；Remove band water device, use decompression distillation dress instead
Put, temperature is risen to 180 DEG C simultaneously, in the reaction decompression distillation of this temperature, detection system simultaneously
Acid number, stopped reaction after acid number is down to 1.5mg/g KOH；Treat that temperature is down to 40～80 DEG C, fast
Speed is poured into seal in drying receptacle and is preserved, and is designated as copolyester polyols sample A3.
Sample A3 is carried out Fourier transform infrared spectroscopy diffraction analysis, and result is similar with Fig. 1,
1733cm-1Near have the stretching vibration peak of C=O, at 2955cm-1Near have the stretching vibration of-OH
Peak and be strong peak.
Measuring the viscosity of sample A3, result is: 2450mPa s.
Measuring the average molecular weight of sample A3, result is: Mn=2355.
Measuring the dispersion of sample A3, result is: DPI=1.40.
The preparation of embodiment 4 low viscosity OH performed polymer sample B1
In raw material, the part by weight of each component is as follows:
Copolyester polyols A1:75 weight portion；
Diluent (polypropylene glycol PPG-3000): 20 weight portions；
Chain extender (1,6-hexanediol): 3 weight portions；
Cross-linking agent (N methyldiethanol amine): 1.5 weight portions；
Catalyst I (dibutyl tin laurate): 0.45 weight portion；
Defoamer (modification organic silicon oil): 0.05 weight portion.
Concrete preparation process is as follows:
First copolyester polyols A1, diluent, chain extender, cross-linking agent are mixed according to the above ratio,
Then heat to 85 DEG C of vacuum drying and remove water 1.5 hours, be hereafter cooled to 45 degrees Celsius, in addition
Stating catalyst I and the defoamer of ratio, 45 degrees Celsius of lower vacuum froth breakings 1 hour, encapsulation preserved,
It is designated as performed polymer B1.
The preparation of embodiment 5 low viscosity OH performed polymer sample B2
In raw material, the part by weight of each component is as follows:
Copolyester polyols A2:85 weight portion；
Diluent (polypropylene glycol PPG-1500): 10.5 weight portions；
Chain extender (BDO): 3 weight portions；
Cross-linking agent (N-ethyldiethanolamine): 1 weight portion；
Catalyst I (N, N '-dimethyl pyridine): 0.40 weight portion；
Defoamer (modification organic silicon oil): 0.1 weight portion.
Concrete preparation process is as follows:
First copolyester polyols A2, diluent, chain extender, cross-linking agent are mixed according to the above ratio,
Then heat to 90 DEG C of vacuum drying and remove water 2 hours, be hereafter cooled to 40 degrees Celsius, add above-mentioned
The catalyst I of ratio and defoamer, 40 degrees Celsius of lower vacuum froth breakings 1.5 hours, encapsulation preserved,
It is designated as performed polymer B2.
The preparation of embodiment 6 low viscosity OH performed polymer sample B3
In raw material, the part by weight of each component is as follows:
Copolyester polyols A3:90 weight portion；
Diluent (polypropylene glycol PPG-2000): 7 weight portions；
Chain extender (1,6-hexanediol): 1.5 weight portions；
Cross-linking agent (diethanolamine): 1 weight portion；
Catalyst I (1,8-diazabicylo 11 carbon-7-alkene): 0.42 weight portion；
Defoamer (modification organic silicon oil): 0.08 weight portion.
Concrete preparation process is as follows:
First copolyester polyols A3, diluent, chain extender, cross-linking agent are mixed according to the above ratio,
Then heat to 100 DEG C of vacuum drying and remove water 2 hours, be hereafter cooled to 50 degrees Celsius, add above-mentioned
The catalyst I of ratio and defoamer, at 50 c vacuum froth breaking 1 hour, encapsulation preserves, note
For performed polymer B3.
Embodiment 7 low viscosity OH performed polymer is for the preparation of no-solvent polyurethane
In raw material, the part by weight of each component is as follows:
OH performed polymer sample B2:100 weight portion；
Isophorone diisocyanate IPDI (isocyanates): 50 weight portions
PCDL: 35 weight portions, number-average molecular weight Mn=3000；
PTMG dihydroxylic alcohols: 22 weight portions, number-average molecular weight Mn=2500；
1,8-diazabicylo 11 carbon-7-alkene (catalyst III): 0.05 weight portion；
1,4-butanediol (chain extender): 0.4 weight portion；
1,6-HD (chain extender): 0.7 weight portion；
Concrete preparation process is as follows:
5g isophorone diisocyanate IPDI, 5.5g Merlon is added in dry there-necked flask
Dihydroxylic alcohols (Mn=3000), 5.5g PTMG dihydroxylic alcohols (Mn=2500), 0.008g 1,8-bis-
Azabicyclic 11 carbon-7-alkene, 0.04g BDO, 0.07g 1,6-hexanediol, in high-speed stirred
(3000rpm) under, reaction mixing 10 minutes, add the OH performed polymer sample of 10g after stopping stirring
B2, is mixing 15 seconds under high-speed stirred (3000rpm), is the most quickly being poured on release paper
Upper doctor blade, is then placed in dry solidification about 10min in the baking oven of 120 degrees Celsius,
Obtain the polyurethane film of solidification.
Embodiment 8 low viscosity OH performed polymer is for the preparation of no-solvent polyurethane
In raw material, the part by weight of each component is as follows:
OH performed polymer sample B3:100 weight portion；
4,4-dicyclohexyl methyl hydride diisocyanate HMDI (isocyanates): 45 weight portions；
PCDL: 30 weight portions, number-average molecular weight Mn=3000；
PTMG dihydroxylic alcohols: 30 weight portions, number-average molecular weight Mn=2500；
1,8-diazabicylo 11 carbon-7-alkene (catalyst III): 0.05 weight portion；
1,4-butanediol (chain extender): 0.2 weight portion；
1,6-HD (chain extender): 0.6 weight portion；
Concrete preparation process is as follows:
5.5g PCDL (Mn=3000), 5.5g poly-tetrahydrochysene furan is added in dry beaker
Mutter ether dihydroxylic alcohols (Mn=2500), 0.008g 1,8-diazabicylo 11 carbon-7-alkene, 0.02g 1,4-
Butanediol, 0.06g 1,6-hexanediol, mix 3 minutes under high-speed stirred (3000rpm), stop
The OH performed polymer sample B3 of 10g is added, the most again at high-speed stirred (3000rpm) after stirring
Lower mixing 15 seconds, is the most quickly poured in release paper by doctor blade, is then placed in 120 degrees Celsius
Baking oven in dry solidification about 10min, i.e. can obtain solidification polyurethane film.
The above, be only several embodiments of the application, and the application not does any type of limit
System, although the application with preferred embodiment disclose as above, but and be not used to limit the application, any
Those skilled in the art, in the range of without departing from technical scheme, utilize above-mentioned taking off
The technology contents shown makes a little variation or modification is all equal to equivalence case study on implementation, belongs to technology
In aspects.
Claims (10)
1. a low viscosity OH performed polymer, it is characterised in that in described low viscosity OH performed polymer
Containing copolyester polyols；
Described copolyester polyols by least one in the dicarboxylic acids with structural formula shown in Formulas I with
At least one polymerization having in the dihydroxylic alcohols of structural formula shown in Formula II obtains:
In Formulas I, n is 0 or 1；A1Selected from the alkylidene that carbon number is 1～8；
In Formula II, m is selected from 0,1,2 or 3；A2Being selected from carbon number selected from carbon number is 1～8
Alkylidene.
Low viscosity OH performed polymer the most according to claim 1, it is characterised in that described common
Viscosity=500 that PEPA is 25 DEG C～3000mPa s；
Number-average molecular weight Mn=2000 of copolyester polyols～3000；
The dispersion PDI=1.2～1.8 of copolyester polyols；
The acid number of copolyester polyols≤1.5mg/g KOH.
3. the method for low viscosity OH performed polymer described in preparation any one of claim 1 or 2, it is special
Levy and be, comprise the following steps:
A) raw material containing copolyester polyols, diluent, chain extender and cross-linking agent is placed in 85～
100 DEG C of vacuum drying；
B) system temperature is down to 40～50 DEG C, after adding catalyst I and defoamer, keeps 40～50 DEG C
At a temperature of vacuum froth breaking no less than 0.5 hour, i.e. obtain described low viscosity OH performed polymer；
Wherein, the weight proportion of used raw material is:
Copolyester polyols: 75～90 weight portions；
Diluent: 5～20 weight portions；
Chain extender: 2～5 weight portions；
Cross-linking agent: 1～3 weight portions；
Catalyst I:0.01～0.5 weight portion；
Defoamer: 0.01～0.1 weight portion.
Method the most according to claim 3, it is characterised in that described diluent is selected from the equal molecule of number
The PolyTHF binary that polypropylene glycol that amount is 200～3000, number-average molecular weight are 1000～2000
Alcohol, number-average molecular weight are at least one in the polypropylene oxide trihydroxylic alcohol of 350～3000.
Method the most according to claim 3, it is characterised in that described chain extender is selected from having Formula II
At least one in the dihydroxylic alcohols of shown structural formula；Described cross-linking agent is selected from alcohol compound and/or hydramine
At least one in compounds.
Method the most according to claim 3, it is characterised in that described catalyst I is selected from tin dilaurate
Dibutyl tin, double (2-dimethylaminoethyl) ether, N, N '-dimethyl pyridine, 1,8-diazabicylo ten
At least one in one carbon-7-alkene.
Method the most according to claim 3, it is characterised in that described copolyester polyols uses ester
Change polycondensation reaction to prepare, comprise the following steps:
(1) by containing at least one having in the dicarboxylic acids of structural formula shown in Formulas I, there is formula
In the dihydroxylic alcohols of structural formula shown in II at least one, the raw material of catalyst II, auxiliary agent be placed in point
In the reaction vessel of water device, N2Under protection, react 2～4 hours at a temperature of 130～150 DEG C,
And remove the water generated in reaction with water entrainer simultaneously；
(2), after step (1) terminates, system temperature is increased to 155～180 DEG C, N2Continue under protection
Continuous reaction also removes the water generated in reaction simultaneously with water entrainer, after reacting 2～4 hours, removes band
Water preparation；
(3), after step (2) terminates, system temperature is increased to 180～200 DEG C of vacuum decompressions except water
2～4 hours, i.e. obtain described copolyester polyols.
Method the most according to claim 7, it is characterised in that step has shown in Formulas I in (1)
The dicarboxylic acids of structural formula with the molar ratio of the dihydroxylic alcohols with structural formula shown in Formula II is:
There is the dicarboxylic acids of structural formula shown in Formulas I: there is the dihydroxylic alcohols of structural formula shown in Formula II
=1:1.0～1.3.
Method the most according to claim 7, it is characterised in that described in there is structural formula shown in Formulas I
At least one in adipic acid, SA, suberic acid of dicarboxylic acids；Described have shown in Formula II
The dihydroxylic alcohols of structural formula is selected from ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, normal hexane
At least one in glycol, diethylene glycol, dipropylene glycol, triethylene glycol；Described catalyst II is selected from
At least one in butyl titanate, tetra isopropyl titanate, metatitanic acid four methyl ester, metatitanic acid orthocarbonate.
10. the method preparing polyurethane material, it is characterised in that by the polyisocyanate containing 45～50 weight portions
Cyanate, 30～35 weight of polyester diatomic alcohol compounds, 25～30 weight portion polyether Glycols chemical combination
Thing, 0.01～1 catalyst III, 0.8～1.1 raw material mix homogeneously of chain extender of weight portion of weight portion,
After adding 100 weight portion low viscosity OH performed polymers mix homogeneously, it is placed in 80～120 DEG C of dry solidifications,
I.e. obtain polyurethane material；
Described low viscosity OH performed polymer selected from described in claim 1 or 2 low viscosity OH performed polymer,
According in the low viscosity OH performed polymer that method described in any one of claim 3 to 9 prepares extremely
Few one.
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| CN114561042A (en) * | 2021-12-28 | 2022-05-31 | 中国科学院福建物质结构研究所 | Compound flame retardant and application thereof as low-thermal-conductivity ablation type flame-retardant and heat-insulating material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6787596B1 (en) * | 1999-10-16 | 2004-09-07 | Skw Bauchemie Gmbh | Solvent-free polyrethane-polymer-hybrid-dispersion and use thereof |
| CN102167949A (en) * | 2010-11-29 | 2011-08-31 | 山东东大聚合物股份有限公司 | HFC-365mfc/227-type environment-friendly polyurethane composite paint and preparation method thereof |
| CN103626951A (en) * | 2012-08-21 | 2014-03-12 | 山东固安特新材料科技股份有限公司 | Special engineering material for reinforcement and preparing method therefor |
| CN104263310A (en) * | 2014-09-19 | 2015-01-07 | 周建明 | Single-component moisture-curing polyurethane adhesive and preparation method thereof |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6787596B1 (en) * | 1999-10-16 | 2004-09-07 | Skw Bauchemie Gmbh | Solvent-free polyrethane-polymer-hybrid-dispersion and use thereof |
| CN102167949A (en) * | 2010-11-29 | 2011-08-31 | 山东东大聚合物股份有限公司 | HFC-365mfc/227-type environment-friendly polyurethane composite paint and preparation method thereof |
| CN103626951A (en) * | 2012-08-21 | 2014-03-12 | 山东固安特新材料科技股份有限公司 | Special engineering material for reinforcement and preparing method therefor |
| CN104263310A (en) * | 2014-09-19 | 2015-01-07 | 周建明 | Single-component moisture-curing polyurethane adhesive and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114561042A (en) * | 2021-12-28 | 2022-05-31 | 中国科学院福建物质结构研究所 | Compound flame retardant and application thereof as low-thermal-conductivity ablation type flame-retardant and heat-insulating material |
| CN114561042B (en) * | 2021-12-28 | 2023-09-29 | 中国科学院福建物质结构研究所 | Compound flame retardant and application thereof as low-thermal-conductivity ablation type flame-retardant heat-insulating material |
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